Demulsifier or water clarifier activity modifiers

ABSTRACT

Adding a cationic starch and/or an anionic starch to a conventional demulsifier or water clarifier reduces activity of the resulting product without losing demulsifier or water clarifier performance.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/503,698 filed May 9, 2017, incorporated herein byreference in its entirety.

TECHNICAL FIELD

The present invention relates to methods and compositions fordemulsifying water and oil emulsions, and more specifically relates tomethods and compositions for modifying demulsifiers to reduce activitywhile maintaining the same performance.

BACKGROUND

The breaking of water-in-crude emulsions is still a challenge in thepetroleum industry. A water-in-oil emulsion results from the mixing of awater-based fluid and crude oil, which are two immiscible fluids. Wateror brine typically accompany crude oil during its recovery from asubterranean reservoir, and additional water may also be added to aid insecondary oil recovery as the well nears the end of production. At therefinery, additional water may be emulsified into the crude oil in aneffort to extract salts and fine solids from the crude oil. Thewater-based fluid may form droplets within the crude oil, i.e. thewater-based fluid droplets are the discontinuous phase, and theoil-based fluid (e.g. crude oil) is the continuous phase.

The presence of the emulsion is beneficial for the extraction process,but it poses major problems for the additional refining steps. Theemulsified water may corrode refinery equipment, such as overheaddistillation columns, and poison catalysts as a result of dissolvedsalts. The viscous emulsions can foul machinery, and entrained solidscan accumulate in certain unit operations. Crude oil may be lost whentrying to dispose or rid the water from the water-in-crude emulsion.

Conventional demulsifiers have characteristics of activity andperformance. Activity is defined herein as the percentage ofintermediates in the final product. Performance is defined herein as howthe demulsifier works in a given system at a particular concentration.

Water clarification may be defined as a process of removing colloidalmaterials from water to recover more pure water. In a non-limitingembodiment, a chemical coagulant, e.g. alum, or a chemical flocculant,e.g. a polymer, or both are added to the water. Colloidal particlesattach to each other and to the additives, and clumps grow to sufficientsize that they can be separated from the water by filtration, gravitysettling, hydrocycloning, or centrifuging. Clarification may be a finalstep in a closed mud system when a clear effluent is needed.

It would be desirable if better demulsifiers, water clarifiers, andmethods for using the same were developed for separating at least aportion of foulants from the water-in-crude emulsions.

SUMMARY

There is provided, in one non-limiting embodiment, a method of modifyingdemulsifier or water clarifier activity that includes adding a cationicstarch and/or an anionic starch to a demulsifier or water clarifier inan amount effective to reduce the activity of the demulsifier or waterclarifier without substantially reducing its performance.

There is additionally provided, in another non-restrictive version, amodified demulsifier or water clarifier that includes a demulsifier orwater clarifier and a cationic starch and/or an anionic starch presentin an amount effective to reduce the activity of the demulsifier orwater clarifier without substantially reducing its performance.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a water drop comparison graph showing milliliters of waterseparated as a function of time for a conventional demulsifier at twodifferent concentrations as compared to the conventional demulsifierhaving a cationic starch added thereto, at the same concentrations;

FIG. 2 is a chart showing the remaining water content of the crude oilafter application of the conventional demulsifier at two differentconcentrations as compared to the conventional demulsifier having acationic starch added thereto, at the same concentrations, used in theFIG. 1 graph;

FIG. 3 is a photograph of two bottles comparing the conventionaldemulsifier (Example 2) with the conventional demulsifier having addedcationic starch (Example 4) at 40° C. after 1 minute;

FIG. 4 is a photograph of the two bottles of FIG. 3 at 40° C. after 10minutes;

FIG. 5 is a photograph in which samples dosed with varying amounts ofdemulsifier and water clarifier are compared to determine of bottle testresults used in screening if a product will work and at what proportion;

FIG. 6 is a photograph of a bottle test with water clarifier todetermine at what dosage the water clarifier works best; the samplesecond from the left exhibited the best water quality;

FIG. 7 is a photograph of a bottle test with incumbent demulsifier (twobottles on left, at two different dosages) compared to new, modifieddemulsifier/water clarifier product (two bottles on right, at twodifferent dosages); the water quality of the modified demulsifier/waterclarifier is better than demulsifier alone;

FIG. 8 is a photograph of an oil carry over analysis at the start of aplant trial without a new product in the system; the oil in watercontent was estimated to be about 3000 ppm;

FIG. 9 is a photograph of an oil carry over analysis during the planttrial. The amount of oil-in-water as visually undetectable; and

FIG. 10 is a chart in which the water content of an oil was comparedamongst three products an experimental Blend 71, and experimental Blend72, and the Incumbent Product A (abbreviated “IP-A”) after allowing 10minutes for separation at ambient temperature. Each product was dosed at25, 50, and 100 ppm. Blend 72 performed better by exhibiting loweroverall water content.

DETAILED DESCRIPTION

It has been discovered that the addition of a cationic starch to aconventional demulsifier or water clarifier allows for the reduction inthe activity of the demulsifier or water clarifier by an unexpectedlygreater amount but without losing the performance of the demulsifier,and rather gaining improved performance and cleaner water. In anon-limiting example, the addition of 1-3 wt % of a cationic starch to aconventional demulsifier will reduce its activity, however, thissynergistic product combination demonstrates a performance greater thanthe conventional demulsifier with activities that are 2× to 2.5×greater. In this example, the final product activity was 19%. In otherwords, the activity reduction is greater than what would be expectedfrom simple dilution; which is defined as synergism herein. That is, thedemulsifier or water clarifier still performs well at the lower activityrate and in some cases, better than the original demulsifier or waterclarifier used alone. Again, activity is defined as the percentage ofactive demulsifier or water clarifier intermediates in the finalproduct. Performance is defined as how the demulsifier or waterclarifier works in a given system at a particular concentration. By“without substantially reducing performance” is meant that performanceis within 10%, alternatively within 5% of the performance without theaddition of the modifier added to the demulsifier or water clarifier.

Normally, to winterize this conventional demulsifier or water clarifierthere are added alcohols and other low freezing point solvents to allowthe material to stay flowable and pumpable at −40° C. Suitable alcoholsand solvents include, but are not necessarily limited to, methanol,isopropyl alcohol, ethylene glycol monobutyl ether, and combinationsthereof. In some cases, DDBSA and/or a cosolvent may be necessary tostabilize a product at low temperatures. Not all demulsifier or waterclarifier products need to be winterized, so in those cases, alcoholsare not required.

Typically, demulsifiers may be used to separate or break emulsions, suchas separating water from oil in a water-in-oil emulsion. Conversely thedemulsifier may separate the oil from an oil-in-water emulsion. The typeof demulsifier used for a particular emulsion may depend on the type ofemulsion, which may be water-in-oil or oil-in-water.

It is believed that the demulsifiers that can be modified by the methodsherein may be any conventional demulsifier, which may number from ten toover 1,000, including, but not necessarily limited to anionicdemulsifiers, cationic demulsifiers, non-ionic demulsifiers, crosslinkeddemulsifiers, acid based demulsifiers, and/or amphoteric demulsifiers.Specific examples include, but are not necessarily limited to,alkylphenol derivatives, ammonium alkylaryl sulfonates, alkylarylsulfonates, alkylarylsulfonate amine salts, amine polymers, epoxyresins, furandione polymers, oxyalkylated alkanolamines, oxyalkylatedalkylphenolic resins, oxyalkylated polyamines, oxyalkylated iminepolymers, oxyalkylated polymers, oxyalkylated polyols, oxyalkylatedether sulfate salts, (methyl) oxirane polymers, phenolic polymers,polyether polyols, polyoxyalkylene glycols, polyurethanes,polyoxyalkylenes, polyethers, polyol esters, polyesters, polyglycoldiepoxides, polyglycol esters, and mixtures thereof. One particularlysuitable demulsifier type is oxyalkylated alkylphenolic resin andpolyoxyalkylene glycol.

Typical water clarifiers may include, but not necessarily be limited to,a polycondensate based on N,N′-bis[3-(dimethylamino)propyl]urea,polyacrylate copolymers, polyacrylamide copolymers,poly(acrylate/acrylamide) copolymers, polycondensate based onalkanolamines, dithiocarbamates, in particular polycondensates based ontriethanolamines, and combinations thereof. Metal ions are also goodwater clarifiers, including, but not necessarily limited to, zinc,aluminum, iron, and zirconium based metal ions. These ions may bepresent in salts including, but not necessarily limited to, zincchloride, zirconium chloride, aluminum chloride, and the like.

Suitable demulsifier or water clarifier activity modifiers include, butare not necessarily limited to, anionic starches and cationic starches.Specific suitable starches include, but are not limited to, biopolymers,plant starches, potato starches, corn starches, rice starches, tapiocastarches, and mixtures thereof. In some non-limiting embodiments, theseare cationic starches and/or an anionic starch with a quaternizedpolyamine.

In one non-limiting embodiment the amount of the modifier added to thedemulsifier or water clarifier ranges from about 0.1 independently toabout 20 wt %, based on the amount of demulsifier or water clarifier;alternatively from about 0.5 independently to about 10 wt %, and inanother non-restrictive version from about 1 independently to about 3 wt%. As used herein with respect to a range, the term “independently”means that any threshold may be used with any other threshold to form asuitable alternative range. For example, the proportion of modifieradded to the demulsifier or water clarifier may range from about 1 toabout 10 wt %, or from about 3 to about 20 wt %.

In one non-limiting embodiment the activity of the demulsifier or waterclarifier is reduced to at least 16%; in a different non-limitingembodiment to at least 13%; alternatively to at least 10%; in anothernon-restrictive form to at least 7%; in another non-restrictive versionto at least 5%; and in another alternative to at least 2%.

There may be an issue in getting the modifier into solution with thedemulsifier or water clarifier without causing separation as themodifier is sensitive to the alcohols that are typically used towinterize a product—that is, keep it stable (non-separating) at lowertemperatures. It has been further discovered that the order of mixingmay be very sensitive in formulating these products; i.e. there may beseparation if the correct order of addition is not followed. However, itis difficult to specify an exact order of addition since the order willdepend on the specific formulation. Some of the blends are not assensitive to the order of addition, whereas others are quite specificthat the solvent needs to be present first, followed by the surfactantstabilizers, and then the modifier, and finally the demulsifier or waterclarifier. Other formulations may have a different order of addition.

Complete separation and/or removal of the water from the water-in-oilemulsion is desirable, but it should be appreciated that completeseparation and/or removal is not necessary for the methods and fluidcompositions discussed herein to be considered effective. Success isobtained if more water is separated from the water-in-oil emulsion byadding the demulsifier to the water-in-oil emulsion as compared to theabsence of the demulsifier. Alternatively, the methods and fluidcompositions described are considered successful if a majority of thewater is separated from the water-in-oil emulsion. Similarly, completewater clarification is not considered the only measure of success, butof course a goal is to clarify water as much as possible.

In a non-limiting embodiment, the water-in-oil emulsion may be awater-in-crude emulsion. The crude-based phase of the emulsion may be aheavy crude, or light oil crude, including but not necessarily limitedto Canadian crude, Venezuelan crude, Murray crude, and the like. Thewater-based phase of the water-in-oil emulsion may be a water-basedfluid or brine-based fluid. In a non-limiting embodiment, thedemulsifier may be added to the water-based phase and/or the oil-basedphase of the water-in-oil emulsion. Alternatively, the demulsifier maybe in a solution with an organic solvent, and the solution may be addedto the oil-based phase (e.g. crude). Other oils that could be in anemulsion treated with the compositions described herein include, but arenot necessarily limited to, shale oil, light oil, medium crudes, heavycrudes, bitumen, and the like.

The effective amount of the demulsifier or water clarifier added to theemulsion may range from about 0.1 ppm independently to about 50,000 ppm,alternatively from about 1 ppm independently to about 3000 ppm, or fromabout 5 ppm independently to about 1000 ppm.

A solvent and/or a second component may be added to the water-in-oilemulsion at the same time or a different time from the demulsifier orwater clarifier. The solvent may be or include, but is not limited to ahydrocarbon-based solvent, an alcohol-based solvent, an organiccarbonate-based solvent, a glycol, a polyglycol, a ketone, an ester, adiepoxide, an acetate, and mixtures thereof. The second component may beor include, but is not limited to a polyol, a diepoxide, andcombinations thereof.

The additive may include the demulsifier or water clarifier in an amountranging from about 5 wt % independently to about 90 wt %, alternativelyfrom about 30 wt % independently to about 70 wt %. The additive mayinclude the solvent in an amount ranging from about 5 wt % to about 90wt %, alternatively from about 20 wt % independently to about 70 wt %.The additive may include a demulsifier (e.g. polyol) in an amountranging from about 1 wt % independently to about 60 wt %, alternativelyfrom about 3 wt % independently to about 20 wt %. The additive mayinclude a demulsifier (e.g. diepoxide) in an amount ranging from about 1wt % independently to about 60 wt %, alternatively from about 3 wt %independently to about 50 wt %.

In a non-limiting embodiment, a treated fluid composition is described.The treated fluid composition may include a water-in-oil emulsion (e.g.water-in-crude emulsion) and a modified demulsifier or water clarifierthat separates water from the oil-in-water emulsion better as comparedto an otherwise identical water-in-oil emulsion absent the demulsifier.The modified demulsifiers and modified water clarifiers described hereinrequire lower doses, are faster, and leave less oil in the water phaseas compared to demulsifiers and water clarifiers that are not modifiedas described.

It will be appreciated that the addition of the modifier to conventionaldemulsifiers or conventional water clarifiers can reduce activity of theproduct without losing performance. That is, the demulsifier or waterclarifier may be used at the same concentration level (e.g. ppm) and getbetter water quality than the original product with higher activity. Forinstance, when the modified demulsifiers or water clarifiers are tested,they give better water quality and better dehydration than the originalproducts that are 50% active; thus there are some synergies when themodifier is added to the demulsifier or water clarifier.

It will be further appreciated that the compositions and methodsdescribed herein can be practiced in the absence of a tannin component,such as those described in U.S. Patent Application Publication No.2016/0032197, incorporated herein by reference in its entirety. Tanninsare described therein as a family of polyphenolic compounds containinghydroxyl groups, and often carboxyl groups; and which in general tend toform complexes with proteins, other organic compounds andmacromolecules.

The invention will be further described with respect to the followingExamples, which are not meant to limit the invention, but rather tofurther illustrate the various embodiments.

EXAMPLES

A Canadian oil that was produced conventionally with a tight emulsionwas used in these Examples. Bottle testing was conducted against acommercially available conventional demulsifier in oil (DMO; ascontrasted with a demulsifier in water which would be designed as aDMW). The DMO was a 50% active product. To the DMO, 3 wt % of a cationicstarch with a quaternized polyamine was added and the concentration ofthe product was reduced. This addition reduced the activity of theproduct to 16%, without a loss in performance, as will be demonstrated.

FIG. 1 is a water drop comparison graph showing milliliters (mL) wateras a function of time for a conventional demulsifier at two differentconcentrations as compared to the conventional demulsifier having thecationic starch added thereto, at the same concentrations, as defined inTable I. It should be noted that the curve for Example 1 is almostentirely covered by the curve for Example 3. FIG. 1 demonstrates thatthe performance of the modified DMO is the same as or very similar tothe non-modified DMO.

TABLE I Convention Demulsifier With and Without Demulsifier ModifierExample Description 1 DMO at 500 ppm 2 DMO at 1000 ppm 3 Modified DMO at500 ppm 4 Modified DMO at 1000 ppm

FIG. 2 is a chart showing the water content for Examples 1 and 2 ascompared to the Examples 3 and 4, at the same concentrations,respectively, used in the FIG. 1 graph. The samples were spun in acentrifuge to ensure that there was no BS (basic sediment) present.Thieved samples were injected into a Karl Fischer titrator to determinethe water content presented in FIG. 2. It may be seen that Example 3gave much lower % water than Example 1; and that Example 4 gave somewhatlower % water than Example 2.

Water quality comparisons are given in FIGS. 3 and 4. FIG. 3 is acomparison of Example 2 (on the left) with Example 4 (on the right) at40° C. after 1 minute. It can be seen that after only one minute Example4 gives noticeably better water quality than Example 2. FIG. 4 is acomparison of Example 2 (on the right) with Example 4 (on the left) at40° C. after 10 minutes. It can also be seen that after ten minutes thedifference in better water quality of Example 4 compared to Example 2 isdramatic.

Thus, it has been discovered that performance of the modified 16% activedemulsifier is comparable, even showing better performance, to the 50%active product. The water quality of the modified demulsifier is muchbetter than that of the conventional demulsifier alone. Further, the newformulation has also been found to be stable at a 60:40 ratio ofwater:methanol for winterizing purposes.

Further Examples

FIGS. 4-10 illustrate a process to optimize or find a “sweet spot” whenmodifying the demulsifiers or water clarifiers using the methodsdescribed herein. In this case, demulsifiers are used.

Photos are best for this explanation, and the final bottle test tellshow the product drops water and the BS&W (basic sediment and water) cutsat a height 10-20 ml above interface.

FIG. 5 is a photograph of bottle test results showing some screening onhow it is determined if a product will work and at what dosage. As canbe seen, the water quality in bottles labelled 100 ppm and 200 ppm lookthe best compared to the rest so this proportion range is the “sweetspot” to work with, where there is some leeway on side where acceptableresults can still be obtained. These tests may be run several times tomake sure repeatable results are obtained.

FIG. 6 shows the bottles after dosing with water clarifier packages asdescribed herein to determine the amount of intermediate required toimprove water quality. As can be seen, the second bottle from the leftis starting to show some good results and again there is a sweet spot,an undertreat and an over treat on either side.

FIG. 7 shows the product that has been built on some different oilcompared to an old product, even though the water drop is a little bitslower the end result turns out dry with minimal oil in water carryover.The experimental product described herein exhibited good performancewhen it was field trialed.

FIG. 8 shows an oil in water analysis before the start of a plant trialwithout the new product in the system. Oil-in-waters were around 3000ppm.

FIG. 9 shows the result of an oil in water analysis after a week oftreating with the oil in water being visually undetectable.

FIG. 10 is a chart showing the water content of the product (Blend 72)after 10 minutes settling at ambient temperature compared to theIncumbent Product A (IP-A); the percentage water is clearly lower forthe Blend 72 product. To support this data, during the field trial thefinal dosage was reduced to 25 ppm after which the sales oil continuedto meet pipeline specification for BS&W (0.5%).

In the foregoing specification, the invention has been described withreference to specific embodiments thereof, and has been described aseffective in providing methods and compositions for separating awater-in-oil emulsion. However, it will be evident that variousmodifications and changes can be made thereto without departing from thebroader scope of the invention as set forth in the appended claims.Accordingly, the specification is to be regarded in an illustrativerather than a restrictive sense. For example, specific demulsifiers,water clarifiers, demulsifier modifiers, heavy crude oils, solvents,alcohols, and the like falling within the claimed parameters, but notspecifically identified or tried in a particular composition or method,are expected to be within the scope of this invention.

The present invention may suitably comprise, consist of or consistessentially of the elements disclosed and may be practiced in theabsence of an element not disclosed. For instance, the method ofmodifying demulsifier or water clarifier activity may comprise, consistessentially of, or consist of adding a cationic starch and/or an anionicstarch to a demulsifier or water clarifier in an amount effective toreduce the activity of the demulsifier or water clarifier withoutsubstantially reducing its performance.

Further, the modified demulsifier or water clarifier composition maycomprise, consist of or consist essentially of a demulsifier or waterclarifier and a cationic starch and/or an anionic starch present in anamount effective to reduce the activity of the demulsifier or waterclarifier without substantially reducing its performance, optionallywith an alcohol.

There may also be provided a method of separating oil and water from anemulsion containing oil and water, where the method comprises, consistsessentially of or consists of introducing a modified demulsifier orwater clarifier to the emulsion in an amount effective to separate atleast a portion of the oil and at least a portion of the water from eachother, where the modified demulsifier or water clarifier comprises,consists essentially of, or consists of a demulsifier or water clarifierand a cationic starch and/or an anionic starch present in an amounteffective to reduce the activity of the demulsifier or water clarifierwithout reducing its performance, and further separating at least aportion of the oil and at least a portion of the water from each other.

As used herein, the terms “comprising,” “including,” “containing,”“characterized by,” and grammatical equivalents thereof are inclusive oropen-ended terms that do not exclude additional, unrecited elements ormethod acts, but also include the more restrictive terms “consisting of”and “consisting essentially of” and grammatical equivalents thereof. Asused herein, the term “may” with respect to a material, structure,feature or method act indicates that such is contemplated for use inimplementation of an embodiment of the disclosure and such term is usedin preference to the more restrictive term “is” so as to avoid anyimplication that other, compatible materials, structures, features andmethods usable in combination therewith should or must be, excluded.

As used herein, the singular forms “a,” “an,” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items.

As used herein, relational terms, such as “first,” “second,” “top,”“bottom,” “upper,” “lower,” “over,” “under,” etc., are used for clarityand convenience in understanding the disclosure and do not connote ordepend on any specific preference, orientation, or order, except wherethe context clearly indicates otherwise.

As used herein, the term “substantially” in reference to a givenparameter, property, or condition means and includes to a degree thatone of ordinary skill in the art would understand that the givenparameter, property, or condition is met with a degree of variance, suchas within acceptable manufacturing tolerances. By way of example,depending on the particular parameter, property, or condition that issubstantially met, the parameter, property, or condition may be at least90.0% met, at least 95.0% met, at least 99.0% met, or even at least99.9% met.

As used herein, the term “about” in reference to a given parameter isinclusive of the stated value and has the meaning dictated by thecontext (e.g., it includes the degree of error associated withmeasurement of the given parameter).

What is claimed is:
 1. A method of modifying demulsifier or waterclarifier activity comprising: adding a cationic starch and/or ananionic starch to a demulsifier or water clarifier in an amounteffective to reduce activity of the demulsifier or water clarifierwithout substantially reducing its performance.
 2. The method of claim 1where the cationic starch and/or an anionic starch is added to ademulsifier and the demulsifier is selected from the group consisting ofalkylphenol derivatives, ammonium alkylaryl sulfonates, alkylarylsulfonates, alkylarylsulfonate amine salts, amine polymers, epoxyresins, furandione polymers, oxyalkylated alkanolamines, oxyalkylatedalkylphenolic resins, oxyalkylated polyamines, oxyalkylated iminepolymers, oxyalkylated polymers, oxyalkylated polyols, oxyalkylatedether sulfate salts, (methyl) oxirane polymers, phenolic polymers,polyether polyols, polyoxyalkylene glycols, polyurethanes,polyoxyalkylenes, polyethers, polyol esters, polyesters, polyglycoldiepoxides, polyglycol esters, and mixtures thereof.
 3. The method ofclaim 1 where the cationic starch and/or an anionic starch is added to awater clarifier and the water clarifier is selected from the groupconsisting of a polycondensate based onN,N′-bis[3-(dimethylamino)propyl]urea, polyacrylate copolymers,polyacrylamide copolymers, poly(acrylate/acrylamide) copolymers,polycondensate based on alkanolamines, triethanolamines, metal ionsselected from the group consisting of zinc, aluminum, iron, zirconium,and combinations thereof, and combinations of these water clarifiers. 4.The method of claim 1 where the effective amount of the cationic starchand/or anionic starch ranges from about 0.1 to about 20 wt %, based onthe demulsifier or water clarifier.
 5. The method of claim 1 where thecationic starch and/or anionic starch comprises a quaternized polyamine.6. The method of claim 1 where activity of the demulsifier is reduced toat least 5%.
 7. The method of claim 1 further comprising adding analcohol to the demulsifier or water clarifier to give a winterizeddemulsifier or water clarifier.
 8. A modified demulsifier or waterclarifier comprising: a demulsifier or water clarifier; and a cationicstarch and/or an anionic starch present in an amount effective to reduceactivity of the demulsifier or water clarifier without reducing itsperformance.
 9. The modified demulsifier or water clarifier of claim 8where the modified compound is a demulsifier and the demulsifier isselected from the group consisting of alkylphenol derivatives, ammoniumalkylaryl sulfonates, alkylaryl sulfonates, alkylarylsulfonate aminesalts, amine polymers, epoxy resins, furandione polymers, oxyalkylatedalkanolamines, oxyalkylated alkylphenolic resins, oxyalkylatedpolyamines, oxyalkylated imine polymers, oxyalkylated polymers,oxyalkylated polyols, oxyalkylated ether sulfate salts, (methyl) oxiranepolymers, phenolic polymers, polyether polyols, polyoxyalkylene glycols,polyurethanes, polyoxyalkylenes, polyethers, polyol esters, polyesters,polyglycol diepoxides, polyglycol esters, and mixtures thereof.
 10. Themodified demulsifier or water clarifier of claim 8 where modifiedcompound is a water clarifier and the water clarifier is selected fromthe group consisting of a polycondensate based onN,N′-bis[3-(dimethylamino)propyl]urea, polyacrylate copolymers,polyacrylamide copolymers, poly(acrylate/acrylamide) copolymers,polycondensate based on alkanolamines, triethanolamines, metal ionsselected from the group consisting of zinc, aluminum, iron, zirconium,and combinations thereof, and combinations of these water clarifiers.11. The modified demulsifier or water clarifier of claim 8 where theeffective amount of the cationic starch and/or an anionic starch rangesfrom about 0.1 to about 20 wt %, based on the demulsifier or waterclarifier.
 12. The modified demulsifier or water clarifier of claim 8where the cationic starch and/or an anionic starch comprises aquaternized polyamine.
 13. The modified demulsifier or water clarifierof claim 8 where activity of the demulsifier or water clarifier isreduced to at least 5%.
 14. The modified demulsifier or water clarifierof claim 8 further comprising an alcohol.
 15. A method of separating oiland water from an emulsion containing oil and water, the methodcomprising: introducing a modified demulsifier or water clarifier to theemulsion in an amount effective to separate at least a portion of theoil and at least a portion of the water from each other, where themodified demulsifier or water clarifier comprises: a demulsifier orwater clarifier; and a cationic starch and/or an anionic starch presentin an amount effective to reduce activity of the demulsifier or waterclarifier without reducing its performance; and separating at least aportion of the oil and at least a portion of the water from each other.16. The method of claim 15 where the effective amount of the demulsifieror water clarifier introduced to the emulsion ranges from about 0.1 ppmindependently to about 50,000 ppm based on the emulsion.
 17. The methodof claim 15 where: when the modified compound is a demulsifier, thedemulsifier is selected from the group consisting of alkylphenolderivatives, ammonium alkylaryl sulfonates, alkylaryl sulfonates,alkylarylsulfonate amine salts, amine polymers, epoxy resins, furandionepolymers, oxyalkylated alkanolamines, oxyalkylated alkylphenolic resins,oxyalkylated polyamines, oxyalkylated imine polymers, oxyalkylatedpolymers, oxyalkylated polyols, oxyalkylated ether sulfate salts,(methyl) oxirane polymers, phenolic polymers, polyether polyols,polyoxyalkylene glycols, polyurethanes, polyoxyalkylenes, polyethers,polyol esters, polyesters, polyglycol diepoxides, polyglycol esters, andmixtures thereof; and when the modified compound is a water clarifier,the starch is added to a water clarifier and the water clarifier isselected from the group consisting of a polycondensate based onN,N′-bis[3-(dimethylamino)propyl]urea, polyacrylate copolymers,polyacrylamide copolymers, poly(acrylate/acrylamide) copolymers,polycondensate based on alkanolamines, triethanolamines, metal ionsselected from the group consisting of zinc, aluminum, iron, zirconium,and combinations thereof, and combinations of these water clarifiers.18. The method of claim 15 where in the modified demulsifier or waterclarifier of claim 9 the effective amount of the cationic starch and/oran anionic starch ranges from about 0.1 to about 20 wt %, based on thedemulsifier or water clarifier.
 19. The method of claim 15 where thecationic starch and/or an anionic starch comprises a quaternizedpolyamine.
 20. The method of claim 15 where activity of the demulsifieror water clarifier is reduced to at least 5%.